Solvent-less ionic liquid epoxy resin

ABSTRACT

Solvent free epoxy system that includes: a hardener compound H comprising: a molecular structure (Y 1 —R 1 —Y 2 ), wherein R 1  is an ionic moiety Y 1  is a nucleophilic group and Y 2  nucleophilic group; and an ionic moiety A acting as a counter ion to R 1 ; and an epoxy compound E comprising: a molecular structure (Z 1 R 2 —Z 2 ), wherein R 1  is an ionic moiety, Z 1  comprises an epoxide group, and Z 2  comprises an epoxide group; and an ionic moiety B acting as a counter ion to R 2 . In embodiments, the epoxy compound E and/or the hardener H is comprised in a solvent-less ionic liquid. The systems can further include accelerators, crosslinkers, plasticizers, inhibitors, ionic hydrophobic and/or super-hydrophobic compounds, ionic hydrophilic compounds, ionic transitional hydrophobic/hydrophilic compounds, biological active compounds, and/or plasticizer compounds. Polymers made from the disclosed epoxy systems and their methods of used.

CROSS REFERENCE TO RELATED APPLICATION

This application is a U.S. National Stage Application under 35 USC 371of International Application No. PCT/US2017/058142 filed on Oct. 24,2017, which claims the priority benefit of the earlier filing date ofU.S. Provisional Application No. 62/412,741, filed Oct. 25, 2016, whichis hereby incorporated by reference in its entirety.

FIELD OF THE DISCLOSURE

The present disclosure relates to novel ionic epoxy resins, systemscontaining such resins, and methods of making or using such resins.

BACKGROUND

Traditional epoxy systems often include thermoset polymers that arewidely used in dental fillings, printed circuit boards, wind turbines,lightweight vehicles, coatings, sheathing, flooring, adhesives,aerospace applications and a variety of other applications. This widerange of applications is facilitated by the availability of variouscuring reactions—and associated chemical compositions andstructures—that provide for desired properties of hardness, flexibility,adhesion, degree of crosslinking, the nature of the interchain bond,high strength (tensile, compressive and flexural), chemical resistance,fatigue resistance, corrosion resistance and electrical resistance.Properties of uncured epoxy resins, such as viscosity, facilitateprocessability by appropriate selection of the monomer, the curingagents, and catalyst. Depending on the source, it is estimated that theworldwide epoxy market could increases from 6.0-7.1 USD billion in 2015to 9.2-10.5 USD billion in 2020 with an average production of 2.5million metric tons per year.

Traditionally, many of the remarkable properties of epoxy systems comeat the cost of significant volatile organic compound (VOC) emissions.Environmental Protection Agency regulations require that at least 80% ofall VOCs are captured in industrial processes, resulting in asignificant impact on overall operational cost together with healthrisks for human operators involved in manufacturing.

SUMMARY

Disclosed is a solvent free ionic epoxy system that includes a hardenercompound H and an epoxy compound E. The hardener compound comprises amolecular structure (Y¹—R₁—Y²), wherein R₁ is an ionic moiety Y¹ is anucleophilic group and Y² nuclophilic group, and an ionic moiety Aacting as a counter ion to R₁. The epoxy compound comprises a molecularstructure (Z¹—R₂—Z²), where R₂ is an ionic moiety, Z¹ comprises anepoxide group, and Z² comprises an epoxide group; and an ionic moiety Bacting as a counter ion to R₂. In embodiments, the epoxy compound Eand/or the hardener H is comprised in a solvent-less ionic liquid, whichsignificantly addresses the issue of VOC in traditional epoxies. Thesystems can further include accelerators, crosslinkers, plasticizers,inhibitors, ionic hydrophobic and/or super-hydrophobic compounds, ionichydrophilic compounds, ionic transitional hydrophobic/hydrophiliccompounds, biological active (BAIL, Biological Active Ionic Liquid)compounds, and/or plasticizer compounds.

Also disclosed are polymers made from the disclosed epoxy systems andtheir methods of used. In certain embodiments, the polymer produced uponpolymerization of hardener compound H and epoxy compound E may haveself-healing properties due to the presence of stable electrical chargesalong to the polymeric chains that drive the healing process throughelectrostatic attraction. In embodiments, a polymer produced uponpolymerization of hardener compound H and epoxy compound E forms ahighly and regular porous system, which could be used but not limited toa filtration membrane, solid electrolyte after replacing the secondaryionic liquid, exchange membrane, etc. In certain embodiments, thepolymer comprises a solid electrolyte, which may be used as electroniccomponent, such as a component of a battery, a capacitor, apiezoelectric material and/or an electro-actuator.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an example of a typical NMR spectra of1,3-di(2′-aminoethylene)-2-methylimidazolium bromide.

FIG. 2 is an example of a typical NMR spectra of,γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy) phenyl]-, methylester benzenebutanoic acid.

FIG. 3 is an example of a typical NMR spectra ofγ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-Benzenebutanoic acid.

FIG. 4 shows the chemical structures of examples of solvent-less ionicliquid epoxy resin and hardener, in accordance with embodimentsdisclosed herein.

FIG. 5 shows the chemical structures of an example of an ionic liquidepoxy system including a super-hydrophobic anionic portion that producesa super-hydrophobic material after the polymerization reaction, inaccordance with embodiments disclosed herein.

FIG. 6 shows the chemical structures of an example ionic liquid epoxysystem including a super-hydrophobic cation that produces asuper-hydrophobic material after the polymerization reaction, inaccordance with embodiments disclosed herein.

FIG. 7 shows the chemical structures of an ionic liquid epoxy systemthat produces a transitional hydrophobic-hydrophilic material after thepolymerization reaction, in accordance with embodiments disclosedherein.

FIG. 8 shows the chemical structures of an ionic liquid epoxy systemthat includes a pharmaceutically active anion and cation and produces amedication release material after the polymerization reaction, inaccordance with embodiments disclosed herein.

FIGS. 9A-9F show the chemical structures of exemplary pharmacologicalactive ions for the solvent-less ionic liquid epoxy resins, FIG. 9A)anti-histamic, FIG. 9B) emollient, FIG. 9C) anti-inflammatory, FIG. 9D)pain reliever, FIG. 9E) anti-inflammatory and FIG. 9F) anti-cholinergic,in accordance with embodiments disclosed herein.

FIGS. 10A-10I show the chemical structures of exemplary ionic liquidexamples FIG. 10A) and FIG. 10B) ionic liquid hardeners, FIG. 10C)self-catalyzed ionic liquid hardener, FIG. 10D) ionic liquidaccelerator, FIG. 10E) ionic liquid epoxy resin, FIG. 10F) ionic liquidaccelerator, FIG. 10G) and FIG. 10H) ionic liquid crosslinker, and FIG.10I) ionic liquid accelerator, in accordance with embodiments disclosedherein.

FIG. 11 shows the chemical structures of examples of hydrophobic anionsusable for the synthesis of ionic liquid epoxides and hardeners, inaccordance with embodiments disclosed herein.

FIG. 12 shows the chemical structures of examples of hydrophobic cationsusable for the synthesis of ionic liquid epoxides and hardeners, inaccordance with embodiments disclosed herein.

FIG. 13 shows the chemical structures of examples of hydrophilic anionsusable for the synthesis of ionic liquid epoxides and hardeners.

FIG. 14 shows the chemical structures of examples of hydrophilic cationsusable for the synthesis of ionic liquid epoxides and hardeners, inaccordance with embodiments disclosed herein.

FIGS. 15A-15F show the chemical structures of examples of biologicalactive ionic liquids (BAILs) to be used as an active material in ionicliquid epoxides systems, FIG. 15A)1-alkyl-1-methylpiperidinium-4-(4-chloro-2-methylphenoxy)butanoate,herbicide; FIG. 15B) cholinium pyrazinate, cytotoxicity, FIG. 15C)Tris(2-hydroxyethyl)methylammonium salicylate,anticoagulant-antiinflammatory, FIG. 15D) ranitidinium docusate,histaminic-emollient, FIG. 15E) lidocainium docusate, painreliever-emollient, FIG. 15F) didecyldimethylammonium ibunoprofenate,antibacterial-anti-inflammatory, in accordance with embodimentsdisclosed herein.

FIGS. 16A-16F show the chemical structures of examples of ionic liquidsused as plasticizers in polymer and epoxides systems. FIG. 16A)1-butyl-3-methylimidazolium tetrafluoroborate, FIG. 16B)1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, FIG. 16C)tetrahexylphosphonium decanoate. FIG. 16D) l-ethylpyridiniumbis(2-ethylhexyl)sulfosuccinate, FIG. 16E) 1-butyl-3-methylimidazoliumhexafluorophosphate, FIG. 16F) 1-octyl-3-methylimidazolium chloride, inaccordance with embodiments disclosed herein.

FIGS. 17A-17D show the chemical structures for BPA-free ionic liquidepoxy systems. FIG. 17A) example of an aliphatic epoxy resin, FIG. 17B)example of an aliphatic hardener, FIG. 17C) second example of analiphatic epoxy resin, and FIG. 17D) Aromatic non phenolic example of anepoxy resin, in accordance with embodiments disclosed herein.

FIGS. 18A and 18B are schematics showing examples of: an electrochemicalcell with a solid electrolyte component (FIG. 18A); and anelectrochemical actuator with a volume change in the electrodes due tothe applied potential (FIG. 18B), in accordance with embodimentsdisclosed herein.

FIG. 19 is a set of cross sectional schematics showing the healingprocess of polymer systems containing fixed charges in the main chainsof the polymer structure. After a mechanical damage is present(cracking), the electrostatic attraction of the charge in the polymerstructure carried out the “healing” of the material, in accordance withembodiments disclosed herein.

FIG. 20 is a set of scanning electron microscope (SEM) images of aJeffamine-BPA film cured in presence of 50% w/w of tetrabutylphosphoniumTFSI ionic liquid. Before the SEM analysis the film was washed withmethanol several times in order to remove the ionic liquid and dried ina vacuum oven (35 C° full vacuum, 48 h), in accordance with embodimentsdisclosed herein.

DETAILED DESCRIPTION

Overview

Various embodiments are based on a realization by the inventors of animproved epoxy chemistry that limits VOC emissions—e.g., at low vaporpressure while retaining the broad applicability of current systems—todramatically reduce processing costs and mitigate associated healthhazards. The present disclosure relates generally to techniques andmechanisms that, according to different embodiments, variously provide asystem of reactive ionic liquids that, when combined, react to formhigh-strength, versatile and/or added-functionality epoxy-basedthermosets. These epoxy systems solve the aforementioned issue of VOCoutgassing.

Some embodiments include synthesizing ionic liquids that, for example,incorporate anions substituted with epoxides (glycidyl groups) on theanion. Another such ionic liquid can contain cations of both diaminesand triamines. Still another such ionic liquids can containmethylated-DABCO cation catalysts. Room-temperature ionic liquids areorganic salts that melt below standard conditions and form solvent-lessliquids with a number of unique physical properties, including zerovapor pressure. There are estimated to be ˜10⁶ likely ion-paircombinations that form ionic liquids. Synthesizing organic salts thatincorporate reactive moieties enable solvent-free and volatile-freechemistry. What follows are a set of example reductions to practice.

To illustrate certain features of various embodiments, solvent-lessionic liquid epoxy systems are variously described with respect to anionic moiety group R₁ and an ionic portion B having respective positivecharges, and further with respect an ionic moiety group R₂ and an ionicportion A having respective negative charges. For example, scheme 1shows a positive R₁ ⁺ substituent in a hardener ionic liquid (IL) andthe negative R₂ ⁻ in the resin IL as one illustrative embodiment.However, in other embodiments, the respective charge signs of ionicmoiety groups R₁, R₂ could be reversed (i.e., wherein the respectivecharge signs of ionic portions A, B are also reversed).

DESCRIPTION OF SEVERAL EMBODIMENTS

Disclosed herein is an epoxy system that includes a hardener compound(H) and an epoxy compound (E). Typically, the hardener compound and theepoxy compound are provided separately and then mixed to form a polymerwhen used. In embodiments, the hardener compound has the molecularstructure according to:Y¹—R₁—Y²,wherein R₁ is an ionic moiety and Y¹ and Y² are bonded to R₁. In certainembodiments Y¹ is, or includes, a nucleophilic group. In certainembodiments Y² is, or includes, a nucleophilic group. In certainembodiments, Y¹ and Y² are identical. In certain embodiments, Y¹ and Y²are non-identical. In specific examples, Y¹ and Y² comprise anucleophile independently selected from: a NH₂ group, a SH group, an OHgroup, a SeH group, and a PH₂ group. In certain embodiments, thehardener compound (H) is part of, such as a component of, a solvent-lessionic liquid, for example as a molecular complex with an ionic moiety Aacting as a counter ion to R₁. Examples of Y¹—R₁—Y₂ are shown in Table 1and FIGS. 4, 5, 6, 7, 8, 10A-10I and 17A-17D. Examples of ionic counterions are shown in FIGS. 4, 5, 6, 7, 8, 9, 10A-10I, 13A-17D.

The disclosed epoxy system further includes an epoxy compound E. Inembodiments the epoxy compound has the molecular structure according to:Z¹—R₂—Z²,where R₂ is an ionic moiety, Z¹ is or includes an epoxide group, and Z²is or includes an epoxide group. In certain embodiments, Z¹ and Z² areidentical. In certain embodiments, Z¹ and Z² are non-identical. Incertain embodiments, the epoxy compound (E) is part of, such as acomponent of a solvent-less ionic liquid, for example as a molecularcomplex with an ionic moiety B acting as a counter ion to R₂. Examplesof Z¹—R₁—Z² are shown in Table 1 and FIGS. 4, 5, 6, 7, 8, 10A-10I and17A-17D. Examples of ionic counter ions are shown in FIGS. 4, 5, 6, 7,8, 9, 10A-10I, 13A-17D.

In certain embodiments the epoxy system further includes one or more ofan accelerator, a crosslinker, a plasticizer, or an inhibitor. Theaccelerator, crosslinker, plasticizer, and/or inhibitor can be includedwith the hardener compound, the epoxy compound, or even as a separatecomponent of the system. Examples of accelerators, crosslinkers,plasticizers, and inhibitors ions are shown in FIGS. 10A-10I and16A-16F.

In certain embodiment, the epoxy system further includes an ionichydrophobic and/or super-hydrophobic compound. In embodiments, the ionichydrophobic and/or super-hydrophobic compound can be provided witheither or both of the epoxy and hardener compound, for example ascounter ion A, the epoxy compound, for example as a counter ion B, orboth for example as a counter ion A and a counter ion B. In embodiments,the ionic hydrophobic and/or super-hydrophobic compound is released asan ionic liquid upon polymerization of hardener compound H and epoxycompound E to modify the properties of a polymer produced. Such ionichydrophobic and/or super-hydrophobic compounds are known in the art andrepresentative examples can found in FIGS. 5 and 6.

In certain embodiment, the epoxy system further includes an ionichydrophilic compound. In embodiments, the ionic hydrophilic compound canprovided with either or both of the hardener compound, for example ascounter ion A, the epoxy compound, for example as a counter ion B, orboth for example as a counter ion A and a counter ion B. In embodiments,the ionic hydrophilic compound is released as an ionic liquid uponpolymerization of hardener compound H and epoxy compound E to modify theproperties of a polymer produced. Such ionic hydrophilic compounds areknown in the art.

In certain embodiment, the epoxy system further includes an ionictransitional hydrophobic/hydrophilic compound. In embodiments, the ionictransitional hydrophobic/hydrophilic compound can provided with eitheror both of the hardener compound, for example as counter ion A, theepoxy compound, for example as a counter ion B, or both for example as acounter ion A and a counter ion B. In embodiments, the ionictransitional hydrophobic/hydrophilic compound is released as an ionicliquid upon polymerization of hardener compound H and epoxy compound Eto modify the properties of a polymer produced. Such ionic transitionalhydrophobic/hydrophilic compounds are known in the art andrepresentative examples can found in FIG. 7.

In certain embodiment, the epoxy system further includes a biologicalactive (BAIL, Biological Active Ionic Liquid) compound. In embodiments,the biological active (BAIL, Biological Active Ionic Liquid) compoundcan provided with either or both of the hardener compound, for exampleas counter ion A, the epoxy compound, for example as a counter ion B. orboth for example as a counter ion A and a counter ion B. In embodiments,the biological active (BAIL, Biological Active Ionic Liquid) compound isreleased as an ionic liquid upon polymerization of hardener compound Hand epoxy compound E to modified the properties of a polymer produced.Such biological active (BAIL, Biological Active Ionic Liquid) compoundsare known in the art and representative examples can found in FIGS. 8,9A-9F, and 15A-15F.

In certain embodiment, the epoxy system further includes a plasticizercompound. In embodiments, the plasticizer compound can provided witheither or both of the hardener compound, for example as counter ion A,the epoxy compound, for example as a counter ion B, or both for exampleas a counter ion A and a counter ion B. In embodiments, the plasticizercompound is released as an ionic liquid upon polymerization of hardenercompound H and epoxy compound E to modify the properties of a polymerproduced. Such plasticizer compounds are known in the art andrepresentative examples can found in FIGS. 16A-16F. In certainembodiments, the plasticizer compound has a low to zero volatility.

Scheme 1

Scheme 1 shows examples of polymerization reactions between a firstcompound and a second compound each including a respective ionic moietygroup and a corresponding counter-ion, in accordance with disclosedembodiments.

More particularly, scheme 1 illustrates examples of a disclosed epoxysystem according to an embodiment. As shown, the epoxy system includes ahardener compound H and an epoxy compound E. As depicted, the hardenercompound H includes a cationic molecular structure (Y¹—R₁—Y²) containingan ionic moiety group R₁ and the Y¹ and Y² groups bonded, for examplechemically bonded to R₁. As shown in the first reaction, the hardenercompound H further includes an anionic portion A⁻, for example, acounter ion, in conjunction with the cationic molecular structure(Y¹—R₁—Y²) at R₁. As shown, the epoxy compound E has an anionicmolecular structure (Z¹—R₂—Z²) that includes an ionic moiety group R₂and two epoxide/electrophilic (represented herein by “Z”) groups bondedto R₂. In addition, the epoxy compound E includes a cationic portion B⁺in conjunction with the anionic molecular structure (Z¹—R₂—Z²), forexample, acting as a counter ion to at R₂. As shown in the secondreaction, the hardener compound H further includes an anionic portionA⁺, for example, a counter ion, in conjunction with the anionicmolecular structure (Y¹—R₁—Y²) at R₁. As shown, the epoxy compound E hasa cationic molecular structure (Z¹—R₂—Z²) that includes an ionic moietygroup R₂ and two epoxide/electrophilic (represented herein by “Z”)groups bonded to R₂. In addition, the epoxy compound E includes ananionic portion B⁻ in conjunction with the anionic molecular structure(Z¹—R₂—Z²), for example, acting as a counter ion to at R₁. As shown inthe third reaction, the hardener compound H further includes an anionicportion A⁻, for example, a counter ion, in conjunction with the cationicmolecular structure (Y¹—R₁—Y²) at R₁. As shown, the epoxy compound E hasa cationic molecular structure (Z¹—R₂—Z²) that includes an ionic moietygroup R₂ and two epoxide/electrophilic (represented herein by “Z”)groups bonded to R₂. In addition, the epoxy compound E includes ananionic portion B⁻ in conjunction with the anionic molecular structure(Z—R₂—Z), for example, acting as a counter ion to at R₂. As shown in thefourth reaction, the hardener compound H further includes a cationicportion A⁺, for example, a counter ion, in conjunction with the cationicmolecular structure (Y¹—R₁—Y²) at R₁. As shown, the epoxy compound E hasa cationic molecular structure (Z¹—R₂—Z²) that includes an ionic moietygroup R₂ and two epoxide/electrophilic (represented herein by “Z”)groups bonded to R₂. In addition, the epoxy compound E includes acationic portion B⁺ in conjunction with the anionic molecular structure(Z¹—R₂—Z²), for example, acting as a counter ion to at R₁.

Unless otherwise indicated, “anionic”—as used as used in the particularcontext of “anionic molecular structure,” “anionic portion,” “anionicmoiety group,” or the like—refers to the characteristic of an atom ormolecular structure (e.g., a molecule or portion thereof) providing anegative charge to facilitate bonding with a positive charge of acounterpart “cationic” structure/portion/group. For example an anionicportion A⁻ can be bonded to ionic moiety group R₁ by an ionic bond(e.g., where A⁻ is a single atom) or by an intermolecular bond, forexample. Alternatively or in addition a cationic portion B⁺ can bebonded to ionic moiety group R₂ by an ionic bond (e.g., where B⁺ is asingle atom) or by an intermolecular bond. In another example ancationic portion A⁺ can be bonded to ionic moiety group R₁ by an ionicbond (e.g., where A⁺ is a single atom) or by an intermolecular bond, forexample. Alternatively or in addition a anionic portion B⁻ can be bondedto ionic moiety group R₂ by an ionic bond (e.g., where B⁻ is a singleatom) or by an intermolecular bond.

In the example reaction pathway shown in scheme 1, Y¹ and/or Y₂ can be anucleophilic group—e.g., including but not limited to, —NH₂, —SH, —OH,—SeH, —PH₂ or other nucleophilic substituent. In a molecular structure(Y¹—R₁—Y²), at least one such Y group can be reactive with an epoxidegroup of molecular structure (Z¹—R₂—Z²) to for a stable chemicalbond—e.g., a dimer formation—in a completed polymerization reaction.

Table 1 shows examples of molecular structures that can be variouslyutilized in respective ionic liquid epoxy systems. It is noted thatsuperscripted numbers (e.g., R¹, R², R³, R⁴, etc.) are used herein toindicate component structure of a moiety group that, for example, isinstead identified using subscripted numbers (e.g., R₁, R₂).

TABLE 1 Examples of possible structures for R₁ and R₂ in scheme 1Possible (Y¹—R₁—Y²) structures Possible (Z¹—R₂—Z²)structures

R¹, R², R³ R⁴ and R⁵ could be any suitable chain. Y¹ and/or Y² could bea nucleophilic group—e.g., including but not limited to —NH₂, —SH, —OH,—SeH, —PH₂. Y¹ and/or Y² and epoxy moieties (epoxy group is an exampleof Z group that could be any electrophilic group suitable to react withY¹ and/or Y² and form a permanent chemical bond) could be exchangedbetween R₁ and R₂. Anionic moieties could be any suitable anionicsubstituent.

As illustrated by the embodiment shown in scheme 1, the Y¹ and/or Y²groups bonded to ionic moiety group R₁ can be amine groups (e.g., whereY¹ and/or Y² is a primary amine group). The hardener compound H canfunction as a hardener to react with the epoxy compound E. A reaction ofcompounds H, E can result in at one of the epoxide groups forming achain with one of the Y¹ and/or Y² groups—e.g., wherein a separateby-product molecule is formed by anionic portion A⁻ and cationic portionB⁺. Certain embodiments variously facilitate a wide variety ofcombinations of R₁, R₂, Z¹ and/or Z², Y¹ and/or Y², A⁻, A⁺, and B⁻, andB⁺ to be chosen from to achieve desired material characteristics, whileproviding significantly reduced VOC byproducts.

In the example embodiments shown in scheme 1, the first compoundincludes an ionic moiety group R₁ and a corresponding counter-ion A,while the second compound includes an ionic moiety group R₂ and acorresponding counter-ion B. The illustrative reaction pathway shown inscheme 1 represents examples of dimer formation from a polymerizationreaction.

Various combinations of ionic moieties R₁ and R₂ groups are possible,and if the corresponding counter-ions (A and B) are carefully selected,the two compounds can form a secondary ionic liquid (A⁻B⁺), limiting oreven avoiding the possibility of VOC emissions from an ionic liquidepoxy system. Also is possible to use same charge ionic liquid resin andionic liquid hardener where a secondary ionic liquid will not be producebut permanent charges remains in the polymeric chains compensate for thecorresponding counter ions, as is shown in the last two examples inscheme 1.

Aspect of the present disclosure concern a polymer produced by thepolymerization of the epoxide system disclosed herein. In embodiments, apolymer produced upon polymerization of hardener compound H and epoxycompound E comprises self-healing properties due to the presence ofstable electrical charges along to the polymeric chains that drive thehealing process through electrostatic attraction. In embodiments, apolymer produced upon polymerization of hardener compound H and epoxycompound E forms a highly and regular porous system, which could be usedbut not limited to as filtration membrane, solid electrolyte afterreplacing the secondary ionic liquid, exchange membrane, etc. Inembodiments, a polymer comprises a solid electrolyte. An electroniccomponent comprising the polymers disclosed herein. In embodiments, theelectronic component is a component of a battery, a capacitor, apiezoelectric material and/or an electro-actuator.

Synthetic Methods

Scheme 2

Scheme 2 shows an example reaction to synthesize a hardener compound ofan epoxy system according to embodiments disclosed herein. Suchreactions can contribute to the manufacture of some or all of thehardener compounds H, for example, as shown in scheme 1.

As shown in scheme 2, the class of diamine imidazolium ionic liquidsprovide amine chemistry that can be used as a hardener in an epoxypolymer system, such as those disclosed herein. For example, theillustrative reactions of scheme 2 provide for synthesis of1,3-di(2′-aminoethylene)-2-methylimidazolium bromide.

The first step of the synthesis is the protection of the amino group inbromo-ethylamine (1) using tritylchloride (2), and substituting theresulting compound (3) in 2-methylimidazole (4) under basic conditions(refluxing in DMF for 12 h) in order to obtain the bi-substitutedintermediate (5), deprotection of amine groups is carried out in acidicmedia in dioxane to obtain the hydrochloride derivative (6), carefulneutralization using NaOH is required in order to obtain the targetcompound (7).

Full proton NMR spectroscopic characterization was obtained for thetarget compound (7) (see FIG. 1) showing proper peaks that correlatewith expected characteristics. The material obtained is a highly viscousbrown liquid. Additional studies indicate that stability of thishardener in a time window of 6 months (storage without inert atmospherein a lab shelf, closed container) without signs of decomposition. Anionic liquid hardener including compound (7) was tested againstcommercially available resins (1:1 mass ratio), without accelerators ormodifiers of the polymerization reaction. The testing revealed that thehardener was effective with a curing temperature of 120° C. for twohours producing a brown solid material.

Scheme 3

Scheme 3 shows an example of a reaction in a process to synthesize anepoxy compound including the anionic molecular structure (Z¹—R₂—Z²) asshown in scheme 1 according to embodiments disclosed herein. As shown,synthesis of phosphinate di-epoxy acid can be produced using a modifiedArbuzov reaction. In the example reaction shown in scheme 3, acidiccompound (9) is neutralized with tetraakyl phosphonium hydroxide inorder to obtain the corresponding phosphonium ionic liquid, where R⁵ canbe an alkyl, such as an alkyl having between 1 and 16 carbon atoms, suchas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16.

Scheme 4

Scheme 4 shows another example of a reaction in a process to synthesizean epoxy compound including the anionic molecular structure (Z¹—R₂—Z²)as shown in scheme 1 according to embodiments disclosed herein. Moreparticularly, scheme 4 shows a synthesis of a bisphenol A diglycidylether (2,2-bis[4-(glycidyloxy)phenyl]propane) analog by addition of anionic moiety into the monomer structure (scheme 4).

Scheme 5

Scheme 5 shows another example of a reaction in a process to synthesizean epoxy compound including the anionic molecular structure Z¹—R₂—Z²) asshown in scheme 1 according to embodiment disclosed herein. In theillustrative di-glycidylation reaction of scheme 5,4-hydroxy-γ-(4-hydroxyphenyl)-γ-methyl-methyl ester benzenebutanoic acid(10) reacts with epichlorohydrin (11) in basic conditions at 100° C. for15 minutes. Such a reaction can result in a yield above 90% ofγ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy) phenyl]-, methylester benzenebutanoic acid (12). A proton NMR analysis of a materialresulting from one such reaction is shown in FIG. 2. FIG. 2 showscharacteristic peaks indicating that compound (12) is the maincomponent.

Scheme 6

Scheme 6 shows another example of a reaction in a process to synthesizean epoxy compound including the anionic molecular structure (Z¹—R₂—Z²)as shown in scheme 1 according to embodiment disclosed herein. Thereactions shown in scheme 6 can be continued from those shown in scheme5, for example.

As shown in scheme 6, the —OMe (oxygen/methyl group) moiety can behydrolyzed—e.g., without requiring further purification—using a NaOH(3eq)/acetone/water mixed at 0° C. and allowed to warm up to roomtemperature for 1.5 h, (scheme 6). Extended reaction time does not showdeviation from the desired product when the reaction was followed byTLC. The free acid derivative (13),γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutanoicacid was obtained in a quantitative yield and fully characterized byproton NMR in CDCl₃.

An example of a typical spectra obtained for compound (13) is shown inFIG. 3. FIG. 3 reveals all the characteristic features of compound (13).The NMR of the reaction product also shows the presence of the solvent(ethyl acetate) used during the purification process.

Scheme 7

Scheme 7 shows another example of a reaction in a process to synthesizean epoxy compound including the anionic molecular structure (Z¹—R₂—Z¹)as shown in scheme 1 according to embodiment disclosed herein. Thereaction shown in scheme 7 can be continued from those shown in scheme6, for example. In order to mitigate the possible of damaging the epoxygroups in compound (13), the ionic liquid formation can be carried outin methanol, using equimolar amounts of tetrabutyl phosphonium hydroxide(14) to neutralized the benzenebutanoic acid proton (scheme 7), andquickly removing the MeOH (15 minutes mixing time) and produced waterunder vacuum (30 mmHg) at 45° C. during 4 h and dried at roomtemperature and full vacuum for 24 h. In a test run of such a process, adark yellow viscous liquid was obtained.

In embodiments, equimolar amounts of the compound (15) ionic liquidresin and the compound (7) ionic liquid hardener can be combined—e.g.,mixed manually at room temperature and poured into a 1.5 ml siliconmold, and placed overnight in a vacuum oven at 120° C. for 12 h.Reaction of the combined compounds (7) and (15) result in a solidmaterial with a greasy feature and rubber-like toughness. It wastheorized that such properties might be related to relatively lowamounts of crosslinking agents in the epoxy system. In order to probethis assumption, a new ionic liquid hardener was prepared. Secondaryionic liquid produce during the polymerization process istetrabutylphosphonium bromide

Scheme 8

Scheme 8 shows an example of a reaction in a process to synthesize anepoxy compound of aliphatic nature:tetrabutylphosphonium salt of2,2-bis(glycidyloxymethyl)propionic acid (21). The synthetic routeincludes 3 steps: alkylation of commercially available2,2-bis(hydroxymethyl)propionic acid (16) with allyl bromide (17) intoluene with NaOH. This reaction requires overnight reflux forcompletion and produce diallyl intermediate (18) in 90%/yield. Theproduct is quite pure and does not require further purification for thenext step. Oxidation the olefinic intermediate (18) to epoxide (20) wasconducted by a standard method with m-chloroperbenzoic acid (19) at roomtemperature overnight. This method requires tedious column purification,but is safe and gives 90% yield of epoxidized product (20). Formation ofthe target ionic liquid epoxy resin (21) was carried out in methanolwith equimolar amounts of tetrabutylphosphonium hydroxide (14), by asimilar method described for compound (15) on Scheme 7.

Scheme 9

Scheme 9 shows an example of a reaction in a process to synthesize anepoxy compound with positively charged heterocyclic core. Such epoxyionic resin can react either with a negatively charged hardener (secondline in Scheme 1) or with similarly positive hardener (third line inScheme 1). In the case of both positively charged components (thirdline) no additional ionic liquid of AB type is formed, which can beuseful for certain properties.

The synthetic route includes 2 steps: alkylation and quaternization ofcommercially available imidazole (22) with 4-bromo-1-butene (23) inusual alkylation conditions (NaHCO₃-acetonitrile, reflux overnight). Thequaternized intermediate (24) was obtained in 99%. The crude product waspure enough and was used for the next step without additionalpurification. Epoxidation of the olefinic quaternized intermediate (24)was conducted under a standard method with m-chloroperbenzoic acid (19)at room temperature overnight. As in the analogous case with aliphaticepoxy ionic resin (Scheme 8, compound 20), the product required tediouscolumn purification. The final yield was about 50%.

Scheme 10

Scheme 10 shows an example of reactions in a process to synthesize ahardener compound of an epoxy system according to an embodiment. In thisexample embodiment, the new hardener is intended to have a multi-branchstructure in order to promote crosslinking between the polymeric chains.N1, N1-bis(2-aminoethyl)-1,2-ethanediamine (compound 26, scheme 10) wasprotected using a BOC (e.g., tert-butyloxycarbonyl) protecting groupunder room temperature conditions and overnight stirring. Protectedcompound (28) was then alkylated using methyl iodide at 120° C. inacetonitrile reflux with overnight stirring, the alkylation reaction wasfollowed by TLC until the complete consumption of (28), solvent and MeI(methyl iodide) excess were remove by rotary evaporation at 45°-50° C.and 30 mmHg during 4 h, followed by drying at room temperature and fullvacuum. It is important to mention that MeI alkylation agent wasselected due to facile access to the reagent, but there are severaloptions to choose from and the final selection could be used to modifythe properties of the whole epoxy resin system. BOC protection wasremoved using HCl-dioxane solution and the remaining acid wasneutralized using NaOH. After this step the final ionic liquid wasobtained by metathesis of the ionic liquid in an aqueous solution ofLiTFSI, inorganic salts were removed by several washes with nanopurewater and rotary evaporation at 50° C. and 15 mmHg for 4 h. Compound(30) 2-amino-N, N-bis(2-aminoethyl)-N-methyl-ethanaminiumbis(trifluoromethane)sulfonamide was obtained as a viscous white liquid,dried for 24 h at room temperature and full vacuum.

Example results of a test reaction with compound (15) and (30) aredescribed herein. More particularly, one gram of 2-amino-N,N-bis(2-aminoethyl)-N-methyl-ethanaminiumbis(trifluoromethane)sulfonamide (30) was mixed manually with one gramof tetrabutylphosphoniumγ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutanoate(15) (molar ratio 1.5:1) and cured at 120° C. for 12 h in a siliconemold, resulting in a hard solid material, pale yellow in color, wherethe secondary ionic liquid produced is tetrabutylphosphoniumbis(trifluoromethane)sulfonamide.

Scheme 11

Scheme 11 shows an example of a reaction to facilitate synthesis of amodifier (e.g., an accelerant or catalyst) for the epoxy systemaccording to an embodiment. Such an accelerant/catalyst can expedite areaction such as that shown in scheme 1.

It is possible to synthesize a modifier of the polymerization reactionas an ionic liquid or ionic compound that will mitigate or even void thepossibility of VOC emissions. One of the most commonly used reactionmodifiers is DABCO, whose catalytic effect in the polymerizationreaction helps to accelerate the process of curing. Although synthesisof ionic DABCO compounds is known, its ionic form has been tested as ananti-microbial agent, but not as polymerization modifier. In oneillustrative embodiment, a dabconium compound can be synthesized, forexample, by direct alkylation of 1,4-diazabicyclo[2.2.2]octane with1-Bromo octane in dichloromethane under reflux conditions and overnightstirring. Octyl Dabconium bromide can be obtained in quantitative yield.

One advantage of this approach to epoxy technology is the possibility oftuning the properties of the ionic liquid produced during thepolymerization reaction in order to give to the final product differentcharacteristics according to the specific use of each material. Thisin-situ modifier could be designed to be hydrophobic or hydrophilic, toact as a plasticizer of the polymer network and/or to be solidified toact as filler. Alternatively or in addition, such an in-situ modifiercan be adapted for use in providing an antibacterial ionic liquid formedical use.

Example Compounds and Epoxy Systems

FIG. 4 shows an example of an epoxy system, according to an embodiment,that includes some or all of the features of that shown in scheme 1.More particularly, FIG. 4 shows one example of a system including asolvent-less epoxy resin (diepoxy phosphinate tetrabutylphosphonium) andhardener (dimethyl amine imidazolium bromide). When a polymerizationreaction of such a system is complete, a resulting ionic liquid obtainedas a by-product can include tetrabutylphosphonium bromide, which in turncan be used—for example—as plasticizer of a polymerizedphosphinate/dimethylamine imidazolium network.

FIG. 5 shows an example of an epoxy system, according to an embodiment,that includes some or all of the features of that shown in scheme 1.More particularly, FIG. 5 shows one example of a possible solvent-lessionic liquid epoxy system. If, for example, a user requires a polymerwith a super hydrophobic surface it is possible to design the hardenerand resin to produce a super hydrophobic ionic liquid after thepolymerization reaction happens, as the case of imidazoliumbis[bis(pentafluoroethyl)phosphinyl]imide ionic liquids, where theanionic portion is the hydrophobic part of the ionic liquid. One suchionic liquid epoxy system is shown in FIG. 5.

FIG. 6 shows an example of an epoxy system, according to an embodiment,that includes some or all of the features of that shown in scheme 1.More particularly, FIG. 6 illustrates an alternative use ofsuper-hydrophobic cations such asTri(n-hexyl)[2-ethoxy-2-oxoethyl]ammonium.

FIG. 7 shows an example of an epoxy system, according to an embodiment,that includes some or all of the features of that shown in scheme 1. Inthe case of the example embodiment shown in FIG. 7, thehydrophobic-hydrophilic character of the final product can be tuned andcan be modified after the polymerization process using ionic liquidswith a transitional hydrophobicity. In this case the hydrophobicity ismodified by the presence of carbon dioxide. In CO₂ free environmentsthis kind of ionic liquid has hydrophobic behavior. When the material isexposed to CO₂ the ionic liquid suffers a transition to a hydrophiliccondition. This phenomenon is reversible and could provide a tunablematerial even after the curing of the epoxy resins. The same behaviorhas been observed in anionic portions derived from pyrazole, imidazoleand triazole.

FIG. 8 shows an example of an epoxy system, according to an embodiment,that includes some or all of the features of that shown in scheme 1. Theproduction of a secondary ionic liquid, after the curing process, can beuseful in various medical, pharmaceutical and/or other important fieldsof application for ionic liquid epoxy resins. Some embodiments variouslyprovide a long term release system for medication—e.g., usingpharmacologically active ionic liquids such as the ones derived fromibuprofenate and lidocainium. Several combinations can be obtained fromthese ionic liquids, according to various embodiments, to open—forexample—the possibility of pain-killer releasing ferules (FIG. 8). Thesecondary ionic liquid thus produced would be lidocainium ibuprofenate.

FIGS. 9A-9F show various examples of anionic portions and cationicportions—e.g., each to variously function as a respective one of anionicportion A⁻ or cationic portion B⁺ of scheme 1, respectively—each of anepoxy system according to an embodiment. Some embodiments variouslyblend epoxy polymer technology with the emerging field of pharmaceuticalactive ionic liquids. FIGS. 9A-9F show some examples of usefultherapeutic materials that can be adapted for use according to variousembodiment.

FIGS. 10A-10I show various examples of hardener compounds, epoxycompounds and modifiers each of an epoxy system according to arespective embodiment. Some or all of the compounds shown in FIGS.10A-10I can each be a component of a respective system having, forexample, some of all of the features of the system shown in scheme 1.

It is important to remark that the existence of a large number ofpossible counter-ions permits the design of a final polymer that is tomeet any of a wide variety of specifications required by the end user ofa solvent-less ionic liquid epoxy system. Combination of the proper ionscould tune polymer properties such as flexibility, hardness,hydrophobicity, curing time, curing temperature, set up secondaryreactions, ionic conductivity, etc. Also, the design of ionic liquidcrosslinking agents, accelerators, and catalysts (examples shown inFIGS. 10A-10I) would guaranty that the whole epoxy system is composed ofzero vapor pressure components.

Due at least in part to some or all such characteristics, it can bepossible, as an example, to produce thermoset solid state electrolytes,important in the development of batteries for the storage of electricalenergy. A solvent-less ionic liquid epoxy system according to someembodiments allows the injection of an electrolyte into the batterystructure, setting up a polymerization reaction to provide a fullypolymerized, ionic liquid filled, solid state electrolyte.

FIG. 11 shows various examples of an anionic portion—e.g., the anionicportion A shown in scheme 1—each of a respective epoxy system accordingto an embodiment. FIG. 12 shows various examples of cationicportions—e.g., the cationic portions B⁺ shown in scheme 1—each of arespective epoxy system according to an embodiment.

As mentioned above, hydrophobic materials could be produced from ionicliquids epoxies with selection of the corresponding counter ions to thehardener and epoxy ionic liquids. A wide variety of hydrophobic anions(FIG. 11) and hydrophobic cations (FIG. 12) are available to facilitateselection of a combination that, according to different embodiments,precisely accommodates a particular desired level of hydrophobicity fora final material.

FIG. 13 shows various examples of an anionic portion—e.g., the anionicportion A⁻ shown in scheme 1—each of a respective epoxy system accordingto an embodiment. As illustrated by the examples shown in FIG. 11, itcan be possible to synthesized epoxides ionic liquids where thesecondary ionic liquid has a prominent hydrophilic character. Manyinorganic anions are highly hydrophilic (FIG. 13) and require bulkyanions to produce ionic liquids.

FIG. 14 shows various examples of a cationic portions—e.g., the cationicportion B shown in scheme 1—each of a respective epoxy system accordingto an embodiment. FIG. 14 illustrates inorganic cations and organiccations with hydrogen bond donor moieties that are also highlyhydrophilic.

FIGS. 15A-15F show various examples of an ionic liquid epoxycompound—e.g., such as that shown in scheme 1—each of a respective epoxysystem according to an embodiment. There is a wide range of biologicallyactive ionic liquids (BAILs), from ionic liquids with herbicidalproperties to ionic liquids with antitumor activity. Some examples areshown in FIGS. 15A-15F. New BAILs are being introduced regularly, andmany of these BAILs can be used as a secondary ionic liquid in the ionicliquid epoxy systems providing a drug-eluding material after the propercuring process. Other examples are the ionic liquids derived fromflufenamic acid (non-steroidal anti-inflammatory drugs) and ampicillin(anti-tumor activity).

FIGS. 16A-16F show various examples byproduct compounds each to beformed by a reaction of a respective epoxy system according to anembodiment. The compounds shown in FIGS. 16A-16F can each be formed, forexample, by the reaction of the anion A with the cation B shown inscheme 1.

Plasticizers are used to modify the mechanical properties of differentpolymers—e.g., changing the rigidity, deformability, elongation;toughness, process viscosity, service temperature and/or the like.Traditionally, there are two types of plasticizers: inner and externalplasticizers. Inner plasticizers are structural modifications to thepolymers that affect its mechanical properties, i.e. copolymerizationmoieties, addition of substituent groups, etc. External plasticizers areadditives incorporated during the polymers processing, that have effecton the crystallinity of the polymers. Organic solvents are usuallyutilized as plasticizers but their efficiency is typically related tothe permanence of the solvent in the polymer structure. Many commonplasticizers dissipate over time—e.g., at a rate depending on parameterssuch as volatility, boiling point, osmotic pressure and solvent power.Due to such problems, ionic liquids—which have relatively very low vaporpressure—can be used as a new class of plasticizers, in someembodiments. Such use can take advantage of better solvent powers,osmotic pressures and low volatility. Some of the ionic liquids used asplasticizers are shown in FIGS. 16A-16F and all of them can be used asthe secondary ionic liquid in the ionic liquid epoxides systems.

FIGS. 17A-17D show various examples of an epoxy compound—e.g., such asthat shown in scheme 1—each of a respective epoxy system according to anembodiment. In recent years it has been discovered that the presence ofBis Phenol A (BPA) in various polymer formulations presents a healthhazard concern. BPAs have been associated/correlated to problems in thereproduction systems of women and men, birth defects in children,metabolic diseases and immune system affectation. For these and/or otherreasons, it is important for manufacturers to have BPA-free options inpolymer production. Since solvent-less ionic liquid epoxide systemaccording to various embodiments have low intrinsic vapor pressure andthe risk of volatile BPAs is relatively low, they can be important inmitigating the possibility of BPA contamination in polymer-basedproducts intended for human use. Aliphatic systems are one example of animplementation that can mitigate BPA problems. Some proposed structuresto mitigate the possibility of BPA byproducts are show in FIGS. 17A-17D.

FIGS. 18A-18B show an example of devices each including a respectiveepoxy material according to an embodiment. For example, the devices ofFIGS. 18A and 18B can each include a respective epoxy material such asone formed by a reaction such at that shown in scheme 1.

Solid electrolytes and electrochemical actuators are closelyrelated—e.g., both systems are generally compromised of a polymericmatrix containing an electrolyte (organic or inorganic salt) between twoelectronic conductors (electrodes). The main difference is that in solidelectrolytes the corresponding chemistries are typically designed tominimize a volume change in the electrodes, the volume change provokedby ion migration due to an applied potential (FIG. 18A), where theelectrolyte concentration is to be constant during the charge anddischarge cycles. On the other hand, in an electrochemical actuator, adifferent effect is desired—e.g., wherein electrode volume andelectrolyte concentration are to change. Accordingly, a differentchemistry can be needed in order to provoke a differential volume changein the electrodes (FIG. 18B), resulting in compression in one side ofthe cell and expansion in the opposite side, this phenomena is used toproduce a movement proportional to the potential difference applied tothe cell.

Ionic liquid epoxide systems according to different embodiments can bevariously adapted for the production of respective ones of solidelectrolytes and electrochemical actuators. Such an epoxide system canfacilitate synthesis of a polymeric matrix (epoxide polymer) with theproduction of a secondary ionic liquid as a byproduct of thepolymerization reaction. A transition between an electrochemical cellwith a solid state electrolyte and an electrochemical actuator can bebased on design-time selection of the secondary ionic liquid ions andthe composition of the electrodes. Also, the presence of theseelectromechanical properties can allow an ionic liquid epoxide system toprovide improved design and development of piezoelectric materials—e.g.,due to a strong correspondence between the mechanical stress in apolymer and an applied electrochemical potential. One possible use forthis technology is the construction of a wide variety of sensors.

Self-Healing Polymer

FIG. 19 shows an example of a self-healing polymer including an epoxymaterial according to a disclosed embodiment, for example, the epoxymaterial formed by a reaction such at that shown in scheme 1.Self-healing polymers are materials capable of repair themselves frommechanical damage, as scratches, punctures, or cracking. There areseveral mechanisms that provide the polymers with the self-healingproperties being the most used the formation of micro-capsules filledwith the monomeric material and catalysts that react after the formationof the mechanical damage. However, there are also polymeric materialsthat consist of ionomeric chains, where the healing process is drive forthe electrostatic attraction of the charges present in the polymersstructure. FIG. 19, shows a cross-sectional illustration of a healingprocess for this kind of system.

The nature of ionic liquid epoxide systems according to some embodimentscan variously enable polymeric chains with fixed charges that are suitedto promote self-healing properties of a material, for example, wherein asecondary ionic liquid produced during the polymerization reaction is toact as a plasticizer improving the mechanical behavior of the finalproduct.

Polymer Films

FIG. 20 shows an example of a film including an epoxy material accordingto disclosed embodiments, for example, the epoxy material formed by areaction such at that is shown in scheme 1.

Modification of epoxide polymers using an ionic liquid can be performedto change curing reaction conditions, such as temperature, time,hardener/resin ratio and/or the like. For example, ionic liquid contentin an epoxy system can be in a range of 2 to 5 parts per hundred rubber(phr) when utilized as a modifier. Ionic liquids can be used in a rangeof 5 to 10 phr to modify the viscosity of some epoxide components duringa curing process. However, with higher ionic liquids contents (around 30to 70% w/w of the total mass), the ionic liquid tends to produce voidspace in the final material. After washing out this ionic liquid, theresulting material is a highly porous solid with porous size in theorder of 10-20 μm (See FIG. 20 SEM image of a Jeffamine-BPA system with50% tetrabutyl phosphonium TFSI ionic liquid). An ionic liquid epoxidesystem according to some embodiments can produce similar results, with afinal product that could be used as a filter structure with a highlyregular porous size. By modifying the ionic liquid content, it can bepossible to selectively design (“tune”) the resulting porous size andselectivity of the filter system.

Although certain embodiments have been illustrated and described herein,it will be appreciated by those of ordinary skill in the art that a widevariety of alternate and/or equivalent embodiments or implementationscalculated to achieve the same purposes may be substituted for theembodiments shown and described without departing from the scope. Thosewith skill in the art will readily appreciate that embodiments may beimplemented in a very wide variety of ways. This application is intendedto cover any adaptations or variations of the embodiments discussedherein. Therefore, it is manifestly intended that embodiments be limitedonly by the claims and the equivalents thereof.

What is claimed is:
 1. A low or solvent free epoxy system comprising: a hardener compound H comprising: a molecular structure (Y¹—R₁—Y²), wherein R₁ is an ionic moiety, Y¹ comprises a nucleophilic group, Y² comprises a nucleophilic group, and including an ionic moiety A acting as a counter ion to R₁; an epoxy compound E comprising: a molecular structure (Z¹—R₂—Z²), wherein R₂ is an ionic moiety, Z¹ comprises an epoxide group, Z² comprises an epoxide group, and including an ionic moiety B acting as a counter ion to R₂; wherein R₁ and R₂ are of opposite charge, ionic moiety A and ionic moiety B are of opposite charge, and wherein R₁ and ionic moiety A are of opposite charge and R₂ and ionic moiety B are of opposite charge; and wherein ionic moiety A and ionic moiety B are capable to form a secondary ionic liquid upon reaction of the hardener compound H with the epoxy compound E.
 2. The epoxy system of claim 1, wherein the epoxy compound E is a solventless ionic liquid.
 3. The epoxy system of claim 1, wherein Y¹ and Y² comprise a nucleophile independently selected from: a NH₂ group, a SH group, an OH group, a SeH group, and a PH₂ group.
 4. The epoxy system of claim 1, wherein the hardener compound H is a solvent-less ionic liquid.
 5. The epoxy system of claim 1, further comprising one or more of an accelerator, a crosslinker, a plasticizer, or an inhibitor.
 6. The epoxy system of claim 1, wherein the secondary ionic liquid comprises an ionic hydrophobic and/or super-hydrophobic compound, the secondary ionic liquid formed upon polymerization of hardener compound H and epoxy compound E to modify the properties of a polymer produced.
 7. The epoxy system of claim 1, wherein the secondary ionic liquid comprises an ionic hydrophilic compound, the secondary ionic liquid formed upon polymerization of hardener compound H and epoxy compound E to modify the properties of a polymer produced.
 8. The epoxy system of claim 1, wherein the secondary ionic liquid comprises an ionic transitional hydrophobic/hydrophilic compound, the secondary ionic liquid formed upon polymerization of hardener compound H and epoxy compound E to modify the properties of a polymer produced.
 9. The epoxy system of claim 1, wherein the secondary ionic liquid comprises a biological active (BAIL, Biological Active Ionic Liquid) compound, the secondary ionic liquid formed upon polymerization of hardener compound H and epoxy compound E to modify the properties of a polymer produced.
 10. The epoxy system of claim 1, wherein the secondary ionic liquid comprises a plasticizer compound, the secondary ionic liquid formed upon polymerization of hardener compound H and epoxy compound E to modify the properties of a polymer produced.
 11. The epoxy system of claim 10, wherein the plasticizer compound has a low to zero volatility.
 12. The epoxy system of claim 1, wherein a polymer produced upon polymerization of hardener compound H and epoxy compound E comprises self-healing properties due to the presence of stable electrical charges along to the polymeric chains that drive the healing process through electrostatic attraction.
 13. The epoxy system of claim 1, wherein a polymer produced upon polymerization of hardener compound H and epoxy compound E forms a highly and regular porous system.
 14. The epoxy system of claim 13, wherein the polymer produced is a filtration membrane, a solid electrolyte, or an exchange membrane.
 15. A polymer produced by the polymerization of the epoxide system of claim
 1. 16. The polymer of claim 15, wherein the polymer comprises a solid electrolyte.
 17. An electronic component comprising the polymer of claim
 16. 18. The electronic component of claim 17, wherein electronic component is a component of a battery, a capacitor, a piezoelectric material and/or an electro-actuator. 